JPWO2013042751A1 - LAMINATE, LAMINATE, MULTILAYER LAMINATE, PRINTED WIRING BOARD AND METHOD FOR PRODUCING LAMINATE - Google Patents

Abstract

A laminate comprising one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer comprises a fiber-containing resin composition comprising a thermosetting resin and a fiber substrate, The laminated body whose board | substrate layer is 10-70 volume% with respect to the whole laminated body. A laminate containing one or more resin cured product layers and one or more glass substrate layers, wherein the resin cured product layer comprises a cured product of a fiber-containing resin composition containing a thermosetting resin fiber substrate. A laminated board, which is a cured resin layer and the glass substrate layer is 10 to 70% by volume with respect to the whole laminated board. The printed wiring board which has the said laminated board and the wiring provided in the surface of the laminated board. The manufacturing method of the said laminated board including the fiber containing resin hardened | cured material layer formation process which forms a fiber containing resin hardened | cured material layer on the surface of a glass substrate.

Description

  The present invention relates to a laminated body and a laminated board suitable for semiconductor packages and printed wiring boards, a printed wiring board using the laminated board, a multilayer laminated board, and a method for producing the laminated board.

In recent years, demands for thinner and lighter electronic devices have become stronger, and semiconductor packages and printed wiring boards are becoming thinner and higher in density. In order to stably mount electronic components corresponding to these reductions in thickness and density, it is important to suppress warpage that occurs during mounting.
One of the main causes of warpage occurring in the semiconductor package during mounting is a difference in thermal expansion coefficient between the laminated plate used in the semiconductor package and the silicon chip mounted on the surface of the laminated plate. For this reason, efforts are being made to bring the coefficient of thermal expansion close to the coefficient of thermal expansion of the silicon chip, that is, to lower the coefficient of thermal expansion, in the laminate for semiconductor packages. Further, since the low elastic modulus of the laminated plate also causes warpage, it is also effective to increase the elasticity of the laminated plate in order to reduce warpage. Thus, in order to reduce the warpage of the laminate, it is effective to reduce the expansion coefficient and increase the elasticity of the laminate.

Various methods for lowering the thermal expansion coefficient and increasing the elasticity of the laminated board are conceivable. Among them, it is known to lower the thermal expansion coefficient of the resin for the laminated board and to increase the inorganic filler in the resin. In particular, the high filling of the inorganic filler is a technique that can be expected to improve the heat resistance and flame retardancy as well as the low thermal expansion coefficient (Patent Document 1). However, increasing the filling amount of the inorganic filler in this way is known to cause a decrease in insulation reliability, insufficient adhesion between the resin and the wiring layer formed on the surface, and press molding failure during the production of the laminate. Therefore, there is a limit to high filling.
In addition, attempts have been made to achieve a low coefficient of thermal expansion by selecting or improving the resin. For example, a method of increasing the crosslink density of the resin for wiring boards and increasing the Tg to reduce the coefficient of thermal expansion is generally used (Patent Documents 2 and 3). However, increasing the crosslinking density shortens the molecular chain between the functional groups, but shortening the molecular chain beyond a certain level has a limit in terms of reaction and causes a problem of causing a decrease in resin strength. . For this reason, there is a limit to the reduction in the coefficient of thermal expansion by the method of increasing the crosslinking density.
As described above, in the conventional laminated plate, a low thermal expansion coefficient and a high elasticity have been achieved by high filling with an inorganic filler and adoption of a low thermal expansion coefficient resin, but the limit has been reached.

  Further, as a method different from the above, a glass film is used as a layer having a coefficient of thermal expansion substantially matching the coefficient of thermal expansion of the electronic component (silicon chip), and the resin and the glass film are pressed and laminated. Attempts have been made to reduce the shock stress (Patent Document 4), but since the elastic modulus of the resin layer is low and the thermal expansion coefficient is high, it is insufficient to realize a low warpage of the substrate.

JP 2004-182851 A JP 2000-243864 A JP 2000-114727 A Japanese Patent No. 4657554

As described above, since the substrate obtained by the manufacturing method of Patent Document 4 still has a low elastic modulus and a high coefficient of thermal expansion, it is insufficient for realizing a low warpage of the substrate.
The present invention has been made in view of such circumstances, and has a low thermal expansion coefficient and a high elastic modulus, can suppress warpage, and is suitable for the production of a laminated board and a multilayer laminated board, and a laminated board that hardly causes cracks. It is an object of the present invention to provide a multilayer laminated board, a printed wiring board using the laminated board and the multilayer laminated board, and a method for producing the laminated board.

In Patent Document 4, there is no description that a fiber base material is contained in a resin in a substrate formed by laminating a glass film and a resin. From the description of Patent Document 4, it is considered that the resin should contain a fiber base material.
That is, in patent document 4, it is set as the essential structure that the thermal expansion effect | action of the whole board | substrate is substantially determined by the glass film (Claim 1 of patent document 4). In view of this, it is necessary to minimize the influence of the resin on the thermal expansion action of the substrate. To that end, it is necessary to keep the elastic modulus of the resin low (if the resin has a high elastic modulus, this high elasticity The thermal expansion effect of the entire substrate is greatly affected by the resin of the rate). On the other hand, when the fiber base material is contained in the resin, the resin has a high elastic modulus. Therefore, from the description of Patent Document 4, it should be avoided that the resin contains a fiber base material.
Moreover, when a fiber base material is contained in the resin of Patent Document 4, it is considered that the glass substrate easily breaks starting from the fiber base material. Also from this point, in patent document 4, it is estimated that it contains avoiding containing a fiber base material in resin.
At present, there is no example of a laminate in which a fiber base material is contained in a resin layer in a laminate of a glass substrate layer and a resin layer as in Patent Document 4.

  Surprisingly, however, the present inventors have conducted extensive research to solve the above problems, and as a result, in the laminate including the resin cured product layer and the glass substrate layer, the resin cured product layer contains a fiber base material. It was found that a laminate having a low thermal expansion coefficient and a high elastic modulus, suppressing warpage, and hardly causing cracks can be obtained.

This invention is completed based on the said knowledge, Comprising: The following [1]-[15] make it a summary.
[1] A laminate including one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer includes a thermosetting resin and a fiber-containing resin composition including a fiber substrate. The laminate in which the glass substrate layer is 10 to 70% by volume with respect to the entire laminate.
[2] The laminate according to [1], wherein the glass substrate layer has a thickness of 30 to 200 μm.
[3] The laminate according to [1] or [2], wherein the fiber-containing resin composition layer includes an inorganic filler.
[4] The inorganic filler is one or more selected from silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. [3] The laminated body as described in.
[5] The laminate according to any one of [1] to [4], wherein the fiber base material is any one or more selected from glass fiber, polyimide fiber, polyester fiber, and polytetrafluoroethylene fiber.
[6] The thermosetting resin is an epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, The laminate according to any one of [1] to [5], which is one or more selected from silicone resins, triazine resins, and melamine resins.
[7] A laminate including one or more resin cured product layers and one or more glass substrate layers, wherein the resin cured product layer is a cured fiber-containing resin composition including a thermosetting resin fiber substrate. A laminated board comprising a cured fiber-containing resin layer, wherein the glass substrate layer is 10 to 70% by volume with respect to the whole laminated board.
[8] The laminate according to [7], wherein the storage elastic modulus at 40 ° C. is 10 GPa to 70 GPa.
[9] The laminated plate according to [7] or [8] obtained by heating the laminated body according to any one of [1] to [6].
[10] A multilayer laminate including a plurality of laminates, wherein at least one laminate is the laminate according to any one of [7] to [9].
[11] A printed wiring board comprising the laminated board according to any one of [7] to [9] and wiring provided on the surface of the laminated board.
[12] A printed wiring board having the multilayer laminated board according to [10] and wiring provided on the surface of the multilayer laminated board.
[13] The method for producing a laminated board according to any one of [7] to [9], including a fiber-containing resin cured material layer forming step of forming a fiber-containing resin cured material layer on the surface of the glass substrate.
[14] The fiber-containing resin cured product layer forming step is a step of laminating and curing a film made of the fiber-containing resin composition on the glass substrate using a vacuum laminator or a roll laminator. The manufacturing method of the laminated board of description.
[15] The laminated plate according to [13], wherein the fiber-containing resin cured product layer forming step is a step of placing and curing the film made of the fiber-containing resin composition on the glass substrate. Production method.

  According to the present invention, laminates and multilayer laminates that have a low thermal expansion coefficient and a high elastic modulus, can suppress warpage, and are less likely to crack, and laminates suitable for manufacturing these laminates and multilayer laminates And the printed wiring board using these laminated boards and multilayer laminated boards, and the manufacturing method of this laminated board can be provided.

It is a typical sectional view of a layered product concerning a 1st embodiment. It is typical sectional drawing of the laminated body which concerns on 2nd Embodiment. It is typical sectional drawing of the laminated body which concerns on 3rd Embodiment. It is typical sectional drawing of the laminated board which concerns on 1st Embodiment. It is typical sectional drawing of the laminated board which concerns on 2nd Embodiment. It is typical sectional drawing of the laminated board which concerns on 3rd Embodiment.

Hereinafter, the laminate, the laminate, the multilayer laminate, the printed wiring board, and the method for producing the laminate of the present invention will be described in detail.
In the present invention, the laminate means that the thermosetting resin that is a constituent component is uncured or semi-cured, and the laminate means that the thermosetting resin that is a constituent component is cured. Means what

[Laminate]
The laminate of the present invention is a laminate comprising one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer contains a thermosetting resin and a fiber substrate. It consists of a resin composition and the said glass substrate layer is 10-70 volume% with respect to the said laminated body whole.
The size of the laminate of the present invention is selected in the range of 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (the length is appropriately applied when used in a roll) from the viewpoint of handleability. preferable. In particular, the width is preferably 25 mm to 550 mm and the length is 25 mm to 550 mm.
The thickness of the laminate of the present invention is preferably selected in the range of 35 μm to 20 mm depending on the application. The thickness of the laminate is more preferably 50 to 1000 μm, still more preferably 80 to 600 μm, still more preferably 100 to 500 μm, and still more preferably 110 to 450 μm.
The laminate of the present invention is a laminate comprising one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer contains a thermosetting resin and a fiber substrate. It consists of a resin composition and the said glass substrate layer is 10-70 volume% with respect to the said laminated body whole.
A laminated board obtained by curing the fiber-containing resin composition layer of the laminate of the present invention to obtain a fiber-containing resin cured material layer is a glass substrate layer having a low thermal expansion coefficient and a high elastic modulus as much as a silicon chip. Therefore, it becomes a thing with a low thermal expansion coefficient and a high elasticity modulus, a curvature is suppressed, and it becomes difficult to produce a crack. In particular, since this laminate has a glass substrate layer with high heat resistance, it has a low thermal expansion property in a temperature range from 100 ° C. to less than Tg of the fiber-containing resin cured product. Moreover, since the fiber base material contains in the fiber-containing resin cured product layer, the fiber-containing resin cured product layer has a low thermal expansion coefficient and a high elastic modulus, and the laminate including the fiber-containing resin cured product layer is Thus, a lower expansion coefficient and a higher elastic modulus are obtained.
Moreover, if the laminated body of this invention has the said structure other than the fiber base material containing resin composition layer of 1 layer or more and the glass substrate layer of 1 layer or more, it will not contain a fiber further. Can have. However, from the viewpoint of reducing the thickness, the laminate is preferably composed of one or more fiber-containing resin composition layers and one or more glass substrate layers. Similarly, it is preferable that the laminated board mentioned later consists of one or more fiber-containing resin cured material layers and one or more glass substrate layers from a viewpoint of reducing thickness.

<Fiber-containing resin composition>
The fiber-containing resin composition of the present invention includes a thermosetting resin and a fiber base material.
≪Thermosetting resin≫
The thermosetting resin is not particularly limited, and examples thereof include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclohexanes. Examples include pentadiene resin, silicone resin, triazine resin, and melamine resin. Among these, an epoxy resin and a cyanate resin are preferable because they are excellent in moldability and electrical insulation.
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , Stilbene type epoxy resin, Triazine skeleton containing epoxy resin, Fluorene skeleton containing epoxy resin, Triphenolphenol methane type epoxy resin, Biphenyl type epoxy resin, Xylylene type epoxy resin, Biphenyl aralkyl type epoxy resin, Naphthalene type epoxy resin, Dicyclopentadiene -Type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl ether compounds of polycyclic aromatics such as anthracene And the like. Moreover, the phosphorus containing epoxy resin which introduce | transduced the phosphorus compound into these epoxy resins is mentioned. Among these, biphenylaralkyl type epoxy resins and naphthalene type epoxy resins are preferred from the viewpoint of heat resistance and flame retardancy. These can be used alone or in combination of two or more.
Examples of the cyanate resin include bisphenol type cyanate resins such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, and tetramethylbisphenol F type cyanate resin, and prepolymers in which these are partially triazine. . Among these, a novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy. These can be used alone or in combination of two or more.
The content of the thermosetting resin contained in the fiber-containing resin composition is in the range of 20 to 80% by mass with respect to the mass of the non-fiber base component excluding the fiber base material from the total amount of the fiber-containing resin composition. It is preferably 25 to 60% by mass, more preferably 25 to 50% by mass, still more preferably 25 to 40% by mass.

≪Fiber base material≫
There is no restriction | limiting in particular as a fiber base material, Organic fiber, such as E glass, D glass, S glass, and Q glass, Organic fibers, such as a polyimide, polyester, and polytetrafluoroethylene, those mixtures, etc. are mentioned. These fiber base materials have shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary. , Alone or in combination of two or more materials and shapes.
The thickness of the substrate is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface is treated with a silane coupling agent or the like, or is mechanically subjected to fiber opening treatment. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability.
The total content of the fiber base material is preferably in the range of 10 to 80% by volume, more preferably 15 to 75% by weight, still more preferably 20 to 70% by weight, based on the total amount of the fiber-containing resin composition. 30-60 mass% is still more preferable, and 30-55 mass% is still more preferable.

≪Inorganic filler≫
The fiber-containing resin composition may further contain an inorganic filler.
When an inorganic filler is contained in the fiber-containing resin composition, the content of the inorganic filler is in the range of 5 to 75% by volume with respect to the non-fiber base component excluding the fiber base from the fiber-containing resin composition. It is preferable that Moreover, 15-70 mass% is more preferable with respect to the non-fiber base material component remove | excluding the fiber base material from the fiber containing resin composition, and, as for content of an inorganic filler, 30-70 mass% is still more preferable.
Examples of the inorganic filler include silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass.
Of these, silica is preferable from the viewpoint of low thermal expansion, and further, the thermal expansion coefficient is as small as about 0.6 ppm / K, and spherical amorphous silica with little decrease in fluidity when highly filled in a resin is used. More preferred.
The spherical amorphous silica preferably has a cumulative 50% particle size of 0.01 to 10 μm, preferably 0.03 to 5 μm.
Here, the cumulative 50% particle diameter is the particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the powder as 100%. It can be measured with a particle size distribution measuring apparatus using
Moreover, a fine wiring can be formed on the fiber-containing resin cured product layer of the laminate by using silica (nanosilica) having an average primary particle size of 1 μm or less as the inorganic filler. The nano silica preferably has a specific surface area of 20 m ² / g or more. Further, from the viewpoint of reducing the surface shape after the roughening treatment in the plating process, the average primary particle size is preferably 100 nm or less. This specific surface area can be measured by the BET method.
The “average primary particle size” here refers to the average particle size of aggregated particles, that is, not the secondary particle size, but the average particle size of single particles that are not aggregated. The average primary particle size can be determined by measuring with, for example, a laser diffraction particle size distribution meter. As such an inorganic filler, fumed silica is preferable.
Furthermore, the inorganic filler is preferably treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance, and is preferably hydrophobized to improve dispersibility.
When forming fine wiring on the fiber-containing resin cured product layer of the laminate, the content of the inorganic filler is 20% by mass or less in the non-fiber component excluding the fiber substrate from the fiber-containing resin composition. It is preferable. When the blending amount is 20% by mass or less, a good surface shape after the roughening treatment can be maintained, and deterioration of plating characteristics and interlayer insulation reliability can be prevented. On the other hand, since the fiber-containing resin composition can be expected to have low thermal expansion and high elasticity by containing an inorganic filler, the inclusion of an inorganic filler is important when low thermal expansion and high elasticity are also considered as well as fine wiring formation. The amount is preferably 3 to 20% by mass.

≪Other ingredients≫
In addition to the above components, this fiber-containing resin composition includes a curing agent, a curing accelerator, a thermoplastic resin, an elastomer, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, and improved adhesion. An agent or the like can be added.
Examples of curing agents include, for example, when epoxy resin is used, polyfunctional phenolic compounds such as phenol novolac and cresol novolac; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; phthalic anhydride, pyromellitic anhydride Acid anhydrides such as maleic anhydride and maleic anhydride copolymers; polyimides can be used. Several kinds of these curing agents can be used in combination.
Examples of curing accelerators include, for example, epoxy resin curing accelerators such as imidazoles and derivatives thereof; organophosphorus compounds; secondary amines, tertiary amines, and quaternary ammonium salts.
Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers.
Antioxidants include hindered phenols and styrenated phenol antioxidants.
Examples of the photopolymerization initiator include photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones.
Examples of fluorescent whitening agents include fluorescent whitening agents such as stilbene derivatives.
Examples of the adhesion improver include a urea compound such as urea silane and an adhesion improver such as a silane coupling agent.

<Fiber-containing resin composition layer>
A fiber containing resin composition layer consists of said fiber containing resin composition. The fiber-containing resin composition layer includes a semi-cured product in addition to an uncured product of the fiber-containing resin composition.
The size of the fiber-containing resin composition layer of the present invention is preferably selected in the range of 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (the length is appropriately applied when used in a roll). In particular, the width of 25 mm to 550 mm and the length of 25 mm to 550 mm are preferable from the viewpoint of handleability.
The thickness per one layer of the fiber-containing resin composition layer of the present invention is preferably selected in the range of 3 μm to 200 μm. From the viewpoint of lowering the thermal expansion and increasing the elastic modulus of the laminate and the laminate, the thickness per layer of the resin composition is preferably 3 to 150 μm, more preferably 10 to 120 μm, and more preferably 20 to 20 μm. More preferably, it is 120 micrometers, and it is still more preferable that it is 25-110 micrometers.
The fiber-containing resin composition layer of the present invention is preferably contained at a rate of 4 to 90% by volume, more preferably 30 to 90% by volume, still more preferably 30 to 85% by volume, based on the entire laminate. More preferably, it is contained at a ratio of 30 to 80% by volume.
Moreover, although the laminated body and laminated board of this invention have the resin composition layer in which at least 1 layer of fiber base material is contained, you may have the resin composition layer which does not contain a fiber base material in addition to that. Absent. The resin composition layer not containing the fiber base material can be used for the purpose of, for example, arranging between the glass layer and the resin composition layer containing the fiber base material to improve the adhesion between the two layers.
The resin content after drying of the fiber-containing resin composition layer is preferably 20 to 90% by mass, more preferably 25 to 85% by mass, further preferably 30 to 80% by mass, and more preferably 40 to 70% by mass. Further preferred is 45 to 70% by mass. When it is 20% by mass or more, processability and handling properties (ease of handling) are improved. When the content is 90% by mass or less, the content of the fiber base material increases, and a laminate obtained by curing the fiber-containing resin composition layer of the laminate has a low coefficient of thermal expansion and high elasticity. In addition, resin content means the amount of components other than the fiber base material in the total amount of a fiber containing resin composition.
Moreover, when an inorganic filler is contained in the fiber-containing resin composition, 5 to 75% by volume of the total amount of the thermosetting resin and the inorganic filler is preferable, and 15 to 70% by volume is more preferable. 30 to 70% by volume is more preferable. When the content of the inorganic filler is 5 to 75% by volume of the total amount of the thermosetting resin and the inorganic filler, the effect of reducing the thermal expansion coefficient is sufficient, and the moldability is appropriate with appropriate fluidity. Excellent. That is, when the content of the inorganic filler is 5% by volume or more, the effect of reducing the coefficient of thermal expansion is sufficient, and when it is 75% by volume or less, the fluidity is increased and the moldability is improved.

<Glass substrate layer>
As the glass substrate constituting the glass substrate layer, the thickness per layer of the glass substrate layer is preferably a thin glass film of 30 to 200 μm from the viewpoint of thinning the laminate and workability, In consideration of practicality such as ease of handling, the thickness is more preferably 30 to 150 μm, and further preferably 80 to 120 μm. The thickness of a glass substrate layer here refers to the average thickness of a glass substrate layer. The average thickness of the glass substrate layer can be measured using a known thickness measuring instrument such as a micrometer or a film thickness measuring instrument. For example, in the case of a rectangular or square glass substrate layer, the thickness of the four corners and the center can be measured using a micrometer, and the average value can be obtained as the average thickness of the glass substrate layer.
Further, as the material for the glass substrate layer, glass such as alkali silicate glass, non-alkali glass and quartz glass can be used, but borosilicate glass is preferred from the viewpoint of low thermal expansion.
The size of the glass substrate layer of the present invention is preferably selected in the range of 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (the length is appropriately applied when used in a roll). In particular, a width of 25 mm to 550 mm and a length of 25 mm to 550 mm are more preferable from the viewpoint of handleability.
As the thermal expansion coefficient of the glass substrate layer is closer to the thermal expansion coefficient (about 3 ppm / ° C.) of the silicon chip, warpage of the laminated plate or the laminated plate obtained from the laminated body may be suppressed, but preferably 8 ppm / ° C. It is below, More preferably, it is 6 ppm / degrees C or less, More preferably, it is 4 ppm / degrees C or less.
The larger the storage elastic modulus of this glass substrate layer at 40 ° C., the better, but it is preferably 20 GPa or more, more preferably 25 GPa or more, and further preferably 30 GPa or more.
The glass substrate layer is preferably 10 to 70% by volume, more preferably 15 to 70% by volume, and still more preferably 20 to 70% by volume with respect to the entire laminate. When the content of the glass substrate layer is 10% by volume or more, it is advantageous to obtain a laminate having low thermal expansion and high elasticity, and conversely, when the content of the glass substrate layer is 70% by volume or less, processing is performed. It is advantageous in terms of the properties and handling properties (ease of handling).

<Support film>
Said laminated body may have a support body film on the surface. About this support body film, it demonstrates in detail in description of the manufacturing method of the following laminated body.

[Manufacturing method of laminate]
There is no restriction | limiting in particular in the manufacturing method of the said laminated body, For example, it can manufacture suitably by laminating | stacking the prepreg which consists of a fiber containing resin composition, and a glass substrate.
As this lamination method, for example, a pressure lamination such as a vacuum lamination or roll lamination described later is suitably applied.
Next, the prepreg and the pressure laminate will be described.
<Prepreg>
The prepreg is impregnated or coated on a fiber base material with the thermosetting resin and, if necessary, the resin composition containing the inorganic filler, and then dried by heating to be B-staged (semi-cured). Is preferably obtained. This B-stage can usually be performed by heating and drying at a temperature of 100 to 200 ° C. for about 1 to 30 minutes.
<Pressure lamination>
A pressure laminate uses a pressure laminator such as a vacuum laminator or a roll laminator to laminate a prepreg laminated body in which a single prepreg or a plurality of (for example, 2 to 20) prepregs are laminated, and a glass substrate. This can be done by laminating. Vacuum lamination and roll lamination can be performed using a commercially available vacuum laminator or roll laminator.
In addition, as a thermosetting resin in said fiber containing resin composition, what melt | dissolves below the temperature at the time of lamination is used suitably. For example, when laminating using a vacuum laminator or a roll laminator, since it is generally performed at 140 ° C. or lower, the thermosetting resin in the fiber-containing resin composition is preferably melted at 140 ° C. or lower.
≪Support film≫
The prepreg used for laminating preferably has a support film disposed on one side.
Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter may be abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and release paper and copper. Examples thereof include metal foil such as foil and aluminum foil. When copper foil is used for the support film, the copper foil can be used as a conductor layer as it is to form a circuit. In this case, examples of the copper foil include rolled copper and electrolytic copper foil, and those having a thickness of 2 μm to 36 μm are generally used. When using a thin copper foil, a copper foil with a carrier may be used in order to improve workability.
The support film may be subjected to a release treatment in addition to the mat treatment and the corona treatment.

  The thickness of the support film is usually 10 μm to 150 μm, preferably 25 to 50 μm. If it is thinner than 10 μm, handling becomes difficult. On the other hand, as described above, since the support film is usually finally peeled or removed, a thickness exceeding 150 μm is not preferable from the viewpoint of energy saving.

≪Specific example of pressure lamination≫
Next, a specific example of the pressure laminating method will be described.
A prepreg with a support film is pressed against a glass substrate while being pressurized and heated. The lamination is preferably performed by preheating a prepreg and a glass substrate as necessary, and laminating at a pressure bonding temperature (laminating temperature) of preferably 60 ° C. to 140 ° C. and a pressure bonding pressure of preferably 1 to 11 kgf / cm ² . Moreover, when using a vacuum laminator, it is preferable to laminate under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll.
As described above, after the prepreg is laminated on the glass substrate, it is cooled to around room temperature. Thus, a laminated body can be manufactured.

[Laminated board]
The laminate of the present invention is a laminate comprising one or more cured resin layers and one or more glass substrate layers, wherein the cured resin layer includes a thermosetting resin fiber substrate. It is a fiber containing resin hardened material layer which consists of hardened | cured material of a composition, and the said glass substrate layer is 10-70 volume% with respect to the said laminated board whole.
The size of the laminate of the present invention is preferably selected in the range of 10 mm to 1000 mm in width and 10 mm to 3000 mm in length (the length is appropriately applied when used in a roll). In particular, a width of 25 mm to 550 mm and a length of 25 mm to 550 mm are more preferable from the viewpoint of handleability.
The thickness of the laminate of the present invention is preferably selected in the range of 35 μm to 20 mm depending on the application. The thickness of the laminate is more preferably 50 to 1000 μm, still more preferably 80 to 600 μm, still more preferably 100 to 500 μm, and still more preferably 110 to 450 μm.
This laminated board preferably has a structure in which the fiber-containing resin composition layer of the above-described laminate is a fiber-containing resin cured product layer. In this case, the details of the glass substrate layer and the fiber-containing resin composition are as described in the description regarding the laminate. Further, the thickness of the fiber-containing cured product layer is preferably equal to the thickness of the fiber-containing composition layer described above, and the ratio of the fiber-containing resin cured product and the glass substrate layer in the laminate is the same as that of the laminate described above. The ratio of the cured fiber-containing resin and the glass substrate layer is preferably the same.

<Fiber-containing cured resin layer>
The thickness of the fiber-containing resin cured product layer is preferably 3 to 200 μm. If it is 3 μm or more, cracking of the laminate is suppressed. When the thickness is 200 μm or less, the thickness of the glass substrate is relatively increased, so that the thermal expansion coefficient and the high elastic modulus of the laminated plate can be reduced. In this respect, the thickness of the fiber-containing resin cured product layer is more preferably 3 to 150 μm, further preferably 10 to 120 μm, still more preferably 20 to 120 μm, and still more preferably 25 to 110 μm. It is. However, since the appropriate range of the thickness of the fiber-containing resin cured product layer differs depending on the thickness of the glass substrate layer and the number of layers, and the type and the number of the fiber-containing resin cured product layers, it can be appropriately adjusted. .
The storage elastic modulus of this fiber-containing resin cured product layer at 40 ° C. is preferably 10 to 80 GPa. A glass substrate layer is protected as it is 10 GPa or more, and the crack of a laminated board is suppressed. When it is 80 GPa or less, the stress due to the difference in thermal expansion coefficient between the glass substrate layer and the fiber-containing resin cured product layer is suppressed, and warpage and cracking of the laminate are suppressed. From this viewpoint, the storage elastic modulus of the fiber-containing resin cured product layer is more preferably 12 to 75 GPa, and further preferably 15 to 70 GPa.
You may have metal foil, such as copper, aluminum, and nickel, on the single side | surface or both surfaces of a laminated board. The metal foil is not particularly limited as long as it is used for electrical insulating material applications.

<Characteristics of laminates>
The storage elastic modulus at 40 ° C. of the laminate is preferably 10 to 70 GPa, more preferably 20 to 60 GPa, still more preferably 25 to 50 GPa, from the viewpoint of suppressing warpage and cracking of the laminate. More preferably, it is 25-45 GPa.
The average thermal expansion coefficient in the range of 50 to 120 ° C. of the laminate is preferably 1 to 10 ppm / ° C., more preferably 2 to 8 ppm / ° C. from the viewpoint of suppressing warpage and cracking of the laminate. More preferably, it is 2-6 ppm / ° C, and still more preferably 2-5 ppm / ° C.
The average coefficient of thermal expansion in the range of 120 to 190 ° C. of the laminate is preferably 1 to 15 ppm / ° C., more preferably 2 to 10 ppm / ° C. from the viewpoint of suppressing warpage and cracking of the laminate. More preferably, it is 2-8 ppm / degreeC, More preferably, it is 2-6 ppm / degreeC.

[Manufacturing method of laminate]
There is no restriction | limiting in particular in the manufacturing method of said laminated board. Next, a specific example of a method for manufacturing a laminated board will be described.
<Example of production by heat curing of a laminate obtained by laminating>
In the laminate obtained by the above-described lamination, the support film can be peeled off as necessary, and then the fiber-containing resin composition layer can be heated and cured to produce a laminate.
The conditions for heat curing are selected in the range of 20 to 80 minutes at 150 to 220 ° C, more preferably 30 to 120 minutes at 160 to 200 ° C. When a support film subjected to a release treatment is used, the support film may be peeled off after being cured by heating.
According to this method, since it is not necessary to pressurize at the time of manufacture of a laminated board, it is controlled that a crack arises at the time of manufacture.

<Example of production by the press method>
Moreover, the laminated board which concerns on this invention can be manufactured by the press method.
For example, a laminate can be produced by curing the laminate obtained by the above-mentioned laminate by heating and pressurizing by a pressing method.
Further, a prepreg laminate formed by superimposing one prepreg or a plurality of prepregs (for example, 2 to 20 sheets) and a glass substrate are laminated, and heated and pressed by a press method to be cured and laminated. Can also be manufactured. At this time, a laminate may be produced by attaching a support film to the surface of the outermost prepreg and then curing by heating and pressurizing by a pressing method.
This pressing method is preferable from the viewpoint of uniform molding, but the lamination conditions may be limited because the glass substrate is easily broken during lamination. On the other hand, as described above, the production method by heat curing (laminating method) of the laminate obtained by laminating is preferable from the viewpoint that the glass substrate is hard to break and easy in production, but the fiber-containing resin composition and Molding may be difficult depending on the properties and content of the fiber substrate. Therefore, it is preferable to use the pressing method and the laminating method properly as necessary.

[Multi-layer laminate and its manufacturing method]
The multilayer laminate of the present invention is a multilayer laminate including a plurality of laminates, and at least one laminate is the aforementioned laminate of the present invention.
There is no restriction | limiting in particular in the manufacturing method of this multilayer laminated board.
For example, a multilayer laminate can be produced by stacking and laminating a plurality of the laminates (for example, 2 to 20). Specifically, using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., the temperature is about 100 to 250 ° C., the pressure is about 2 to 100 MPa, and the heating time is about 0.1 to 5 hours. Can be molded.

[Printed wiring board and manufacturing method thereof]
The printed wiring board of this invention has said laminated board or multilayer laminated board, and the wiring provided in the surface of the laminated board or multilayer laminated board.
Next, a method for manufacturing this printed wiring board will be described.

<Formation of via holes>
The above laminated plate is drilled by a method such as drilling, laser, plasma, or a combination thereof as necessary to form a via hole or a through hole. As the laser, a carbon dioxide laser, a YAG laser, a UV laser, an excimer laser, or the like is generally used.

<Formation of conductor layer>
Next, a conductor layer is formed on the fiber-containing resin composition layer of the laminate by dry plating or wet plating.
As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used.
In the case of wet plating, first, the surface of the cured fiber-containing resin composition layer is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid ( That is, a roughening treatment is performed with an oxidizing agent such as a mixture of hydrogen peroxide and sulfuric acid) and nitric acid to form uneven anchors. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
In addition, when using what has the support body film which consists of metal foil on the surface as a laminated body, the formation process of this conductor layer can be skipped.

<Formation of wiring pattern>
As a subsequent pattern formation method, for example, a known subtractive method or semi-additive method can be used.

[Multilayer printed wiring board and manufacturing method thereof]
As one form of the printed wiring board described above, a multilayer printed wiring board may be formed by laminating a plurality of laminated boards on which wiring patterns are formed as described above.
In order to manufacture this multilayer printed wiring board, a multilayer is formed by laminating a plurality of laminated boards on which the above wiring patterns are formed via the above-mentioned adhesive film. Thereafter, through holes or blind via holes are formed by drilling or laser processing, and interlayer wiring is formed by plating or conductive paste. In this way, a multilayer printed wiring board can be manufactured.

[Laminated plate and multilayer laminated plate with metal foil, and methods for producing them]
The laminate and multilayer laminate may be a laminate with a metal foil and a multilayer laminate having a metal foil such as copper, aluminum or nickel on one or both sides.
There is no restriction | limiting in particular in the manufacturing method of this laminated sheet with metal foil. For example, as described above, a laminate with a metal foil can be produced by using a metal foil as the support film. Moreover, the laminated body obtained by the said lamination is laminated | stacked by the structure which laminated | stacked 1 sheet or several sheets (for example, 2-20 sheets), and has arrange | positioned metal foil on the single side | surface or both surfaces, A laminated board with metal foil is obtained. It can also be manufactured.
The molding conditions can be applied to a laminate for an electrical insulating material or a multilayer board, for example, using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 100 to 250 ° C., a pressure of 2 Molding can be performed in a range of about 100 MPa and a heating time of about 0.1 to 5 hours.

<Evaluation method of thermal expansion coefficient>
The thermal expansion coefficient of the laminated plate can be measured by using a thermomechanical analyzer (TMA: Thermal Mechanical Analysis), a temperature-dependent three-dimensional displacement measuring device (DIC: Digital Image Correlation), a laser interferometry, or the like.
<Evaluation method of elastic modulus>
The elastic modulus of the laminated plate can be measured as a bending elastic modulus as a static elastic modulus, including measurement of storage elastic modulus using a wide area viscoelasticity measuring device. The bending elastic modulus can be obtained by performing a three-point bending test.

[Laminated structure of laminated body]
As described above, the laminated structure of the laminated body is not particularly limited as long as it is a laminated structure including one or more resin composition layers and one or more glass substrate layers.
For example, as shown in FIG. 1, a laminate 10 having a five-layer structure in which a resin composition layer 11a, a resin composition layer 11b, a glass substrate layer 12, a resin composition layer 11c, and a resin composition layer 11 are laminated in this order. There may be.
Moreover, the laminated body 20 of the 3 layer structure formed by laminating | stacking the resin composition layer 21a, the glass substrate layer 22, and the resin composition layer 21b in this order may be sufficient as FIG.
Further, as shown in FIG. 3, the laminate 30 has a five-layer structure in which a resin composition layer 31a, a glass substrate layer 32a, a resin composition layer 31b, a glass substrate layer 32b, and a resin composition layer 31c are laminated in this order. May be.

[Laminated structure of laminated plates]
As described above, the laminated structure of the laminated plate is not particularly limited as long as it is a laminated structure including one or more cured resin layers and one or more glass substrate layers.
For example, as shown in FIG. 4, a laminated board 110 having a five-layer structure in which a cured resin layer 111a, a cured resin layer 111b, a glass substrate layer 112, a cured resin layer 111c, and a cured resin layer 111 are stacked in this order. There may be.
Moreover, as shown in FIG. 5, the laminated board 120 of the 3 layer structure formed by laminating | stacking the resin cured material layer 121a, the glass substrate layer 122, and the resin cured material layer 121b in this order may be sufficient.
In addition, as shown in FIG. 6, a laminated board 130 having a five-layer structure in which a cured resin layer 131a, a glass substrate layer 132a, a cured resin layer 131b, a glass substrate layer 132b, and a cured resin layer 131c are laminated in this order. May be.

Next, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited to these descriptions.
In the examples and comparative examples, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.

[Production of a resin composition solution having an unsaturated maleimide group]
In a reaction vessel with a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 4,4′-bis (4-aminophenoxy) biphenyl: 69.10 g, bis (4 -Maleimidophenyl) sulfone: 429.90 g, p-aminophenol: 41.00 g, and propylene glycol monomethyl ether: 360.00 g, reacted at reflux temperature for 2 hours to have an acidic substituent and an unsaturated maleimide group A solution of the resin composition was obtained.

[Production of varnish containing thermosetting resin composition]
(1) As a curing agent (A), a solution of a resin composition having the unsaturated maleimide group,
(2) As the thermosetting resin (B), a bifunctional naphthalene type epoxy resin [manufactured by Dainippon Ink & Chemicals, trade name, HP-4032D],
(3) As modified imidazole (C), isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd., trade name: G8009L],
(4) As inorganic filler (D), fused silica [manufactured by Admatech Co., Ltd., trade name: SC2050-KC, concentration 70%, average particle size of primary particles: 500 nm, specific surface area by BET method: 6.8 m ² / G],
(5) As phosphorus-containing compound (E) that imparts flame retardancy, phosphorus-containing phenol resin [manufactured by Sanko Chemical Co., Ltd., trade name: HCA-HQ, phosphorus content: 9.6% by mass],
(6) As the compound (F) capable of chemical roughening, crosslinked acrylonitrile butadiene rubber (NBR) particles [manufactured by JSR Corporation, trade name: XER-91],
(7) As a diluent solvent, methyl ethyl ketone,
Were mixed at a blending ratio (parts by mass) shown in Table 1 to prepare a uniform varnish (G) having a resin content (total of resin components) of 65% by mass and a solvent of 35% by mass.

[Manufacture of prepreg]
The above-mentioned varnish (G) was impregnated and coated on E glass cloths having different thicknesses and dried by heating at 160 ° C. for 10 minutes to obtain 250 mm × 250 mm prepregs. As the type of E glass cloth, three types of IPC standards 1027, 1078, and 2116 of Asahi Kasei E-materials were used. The resin contents of the prepregs produced using these three types of glass cloth (sometimes referred to as PP # 1027, PP # 1078, and PP # 2116, respectively) were 66, 54, and 50% by mass, respectively. It was. Moreover, E glass cloth content of these prepregs was 34, 46, and 50 mass%, respectively.

[Examples 1 to 6 and Comparative Example 1]
As a glass film, a 50 μm thick glass film “trade name OA-10G” (manufactured by Nippon Electric Glass Co., Ltd., 250 mm × 250 mm) and a 100 μm thick glass film “trade name OA-10G” (Nippon Electric Glass Co., Ltd.) , 250 mm × 250 mm) (which may be referred to as GF50 μm and GF100 μm, respectively).
The glass film and the prepreg are overlaid as shown in Table 2, and an electrolytic copper foil with a thickness of 12 μm is placed up and down, and pressed at a pressure of 3.0 MPa and a temperature of 235 ° C. for 120 minutes to obtain a copper-clad laminate. A plate was made.

[Measurement]
About the laminated board obtained by said Example and comparative example, performance was measured and evaluated with the following method.
(1) Measurement of coefficient of thermal expansion A test piece of 4 mm × 30 mm was cut out from the laminate. When using a copper clad laminated board, after removing copper foil by being immersed in copper etching liquid, the test piece was cut out.
Using a TMA test apparatus (manufactured by DuPont, TMA2940), it was evaluated by observing the thermal expansion characteristics of the test piece below Tg. Specifically, the temperature rise rate is 5 ° C./min, 1st run, measurement range is 20 to 200 ° C., 2nd run measurement range is −10 to 280 ° C., weight is 5 g, and chuck is 10 mm. The average coefficient of thermal expansion in the range of ° C and in the range of 120 to 190 ° C was determined. The results are shown in Table 2.
(2) Measurement of storage elastic modulus A test piece of 5 mm × 30 mm was cut out from the laminate. When using a copper clad laminated board, after removing copper foil by being immersed in copper etching liquid, the test piece was cut out.
Using a wide-area viscoelasticity measurement device (DVE-V4, manufactured by Rheology), measuring the tensile storage modulus at 40 ° C under the conditions of 20 mm span, 10 Hz frequency, and 1-3 μm vibration displacement (stop excitation) did. The results are shown in Table 2.

  As is apparent from Table 2, Examples 1 to 6 of the present invention containing a glass film are excellent in low thermal expansion at 50 to 120 ° C. and high elasticity at 40 ° C. as compared with Comparative Example 1 not containing a glass film. . Also, in the high temperature region of 120 to 190 ° C., the coefficient of thermal expansion is higher in Comparative Example 1 than in the low temperature region (50 to 120 ° C.), whereas in Examples 1 to 6, it is almost the same as the low temperature region. It can be seen that it has a low thermal expansion property. Therefore, Examples 1 to 6 of the present invention maintain low thermal expansibility not only in the low temperature region but also in the high temperature region.

DESCRIPTION OF SYMBOLS 10 Laminated body 11a, 11b, 11c, 11d Resin composition layer 12 Glass substrate layer 20 Laminated body 21a, 21b Resin composition layer 22 Glass substrate layer 30 Laminated body 31a, 31b, 31c Resin composition layer 32a, 32b Glass substrate layer 110 Laminated plate 111a, 111b, 111c, 111d Resin cured product layer 112 Glass substrate layer 120 Laminated plate 121a, 121b Resin cured product layer 122 Glass substrate layer 130 Laminated plate 131a, 131b, 131c Resin cured product layer 132a, 132b Glass substrate layer

Claims (15)

A laminate including one or more resin composition layers and one or more glass substrate layers,
The resin composition layer is composed of a fiber-containing resin composition including a thermosetting resin and a fiber base material,
The laminated body whose said glass substrate layer is 10-70 volume% with respect to the said whole laminated body.   The laminate according to claim 1, wherein the glass substrate layer has a thickness of 30 to 200 μm.   The laminate according to claim 1 or 2, wherein the fiber-containing resin composition layer includes an inorganic filler.   The inorganic filler is one or more selected from silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. Laminated body.   The laminate according to any one of claims 1 to 4, wherein the fiber base material is at least one selected from glass fiber, polyimide fiber, polyester fiber, and polytetrafluoroethylene fiber.   The thermosetting resin is epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, The laminate according to any one of claims 1 to 5, wherein the laminate is one or more selected from a triazine resin and a melamine resin. A laminate comprising one or more cured resin layers and one or more glass substrate layers,
The resin cured product layer is a fiber-containing resin cured product layer made of a cured product of a fiber-containing resin composition containing a thermosetting resin fiber substrate,
The laminated board whose said glass substrate layer is 10-70 volume% with respect to the said laminated board whole.   The laminate according to claim 7, wherein the storage elastic modulus at 40 ° C is 10 GPa to 70 GPa.   The laminated board of Claim 7 or 8 obtained by heating the laminated body of any one of Claims 1-6. A multilayer laminate comprising a plurality of laminates,
The multilayer laminated board whose at least 1 laminated board is a laminated board of any one of Claims 7-9.   The printed wiring board which has a laminated board of any one of Claims 7-9, and the wiring provided in the surface of the said laminated board.   The printed wiring board which has a multilayer laminated board of Claim 10, and the wiring provided in the surface of the said multilayer laminated board.   The manufacturing method of the laminated board of any one of Claims 7-9 including the fiber containing resin hardened | cured material layer formation process which forms a fiber containing resin hardened | cured material layer on the surface of a glass substrate.   The lamination according to claim 13, wherein the fiber-containing resin cured product layer forming step is a step of laminating and curing a film made of the fiber-containing resin composition on the glass substrate using a vacuum laminator or a roll laminator. A manufacturing method of a board.   The method for producing a laminated board according to claim 13, wherein the fiber-containing resin cured product layer forming step is a step of pressing and curing after disposing a film made of the fiber-containing resin composition on the glass substrate.